Ether-amines used as gelatin hardeners



United States Patent 3,408,198 ETHER-AMINES USED AS GELATIN HARDENERS Delbert D. Reynolds and John F. Tinker, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Aug. 28, 1962, Ser. No. 220,031 29 Claims. (Cl. 96-111) This invention relates to the hardening of gelatin with ether-amines characterized in that each molecule thereof has a ROCH NR' group therein, R and R each being alkyl or alkylene.

In the photographic art investigators are always on the lookout for compounds which satisfactorily harden photographic gelatin, are photographically inert, and of sufiicient structure that they do not migrate to any appreciable extent from one layer to another.

One object of our invention is to provide hardeners for gelatin which are polyfunctional and contain alkoxymethylamine groups therein. Another object of our invention is to provide hardeners for gelatin which are photographically inert. A further object of our invention is to provide gelatin hardeners which resist migration from layer to layer. Other objects of our invention will appear herein.

We have found that certain alkoxymethylamines which are polyfunctional in nature are useful as hardeners for gelatin and are particularly useful within the range of concentration of 15% based on the weight of the gelatin. However, even in lesser or greater concentrations these alkoxymethylamines have an effect on the gelatin in that the resistance to swelling is increased and the gelatin layers prepared fiom compositions containing the same are considerably more resistant to water at an elevated temperature than gelatin layers containing no hardener.

The gelatin hardeners which are useful for mixing with gelatin to form compositions in accordance with our invention are polyfunctional alkoxymethylamines having for each unit or molecule the group ROCH N--R in which R and R are each either alkyl or alkylene. The invention contemplates as hardening compounds both those having ring nitrogens and aliphatic-type compounds containing alkoxymethylamine structures therein. Although the preferred amount of hardener for use is 1-5% based on the weight of the gelatin, in some cases it may be desirable to use amounts of hardener outside of these limits which amounts have a hardening effect. The percentage of hardener to use will be governed to some extent by the degree of hardening desired in the gelatin layer. A large portion of the compounds useful for hardening gelatin may be referred to as bifunctional alkoxymethylamines. However, in the case of certain ring structures, this language loosely applies to the compounds which are useful.

The compounds useful as hardeners are conveniently prepared by reacting an amine either a simple amine or a polyfunctional amine with formaldehyde in the presence of an alcohol. In some cases, the alcohols may be built into amines. In those instances, further alcohol need not be supplied for the reaction to go in the desired manner. The use of compounds which have been quaternized is outside of our invention.

The hardening agents in accordance with our invention may be in the form of polymers such as made up of a number of recurring units or they may be compounds of a more simple type. A great number of the compounds contemplated in accordance with our invention as being useful for gelatin hardeners are of the water-soluble type which contributes to good miscibility with aqueous gelatin solutions. The invention also in- 3,408,198 Patented Oct. 29, 1968 ice eludes compounds in accordance with our invention which are water-insoluble and it is desirable that these be used in the form of their aqueous dispersions or in the form of solvent solutions when supplied to aqueous solutions of gelatin.

One type of compounds useful as hardeners for gelatin are those having the following formulae: [-O(CH2)nOOH2N NCfl-H]; or [-o(onanocHn wnnml rom-lx in which R is H or lower alkyl, n and m are numbers from 2 to 10 and x is a number which may extend up to 500, 1,000 or even more. Another type of compounds useful for hardening in accordance with our invention is the alkoxymethyl heterocyclic amines; the following two compounds being representative of compounds of this nature:

CH2 CH2 CH3 HTNoH2ooH, 3H 0 H3 3-isobutoxymethyl oxazolidine 0 N 0 H. E EH.

H5011 5-hydroxymethyl-3,7-dioxa-1-azabicyclo [3,3 ,0] octane Other types of compounds which are useful as hardeners in photographic emulsions in accordance with our invention are those of the open-chain type; the following being an example:

CH3 (3H3 CH3 CH OHCHzOCHr-N-CH:OOH:(JHCH3 N,N-bis(isobutoxymethyl)methylamine Instead the nitrogen may be supplied in the form of a piperazine configuration or a di-sec. amine, the remainder of the compound being linear. The following illustrates the types of compounds:

CHaCHgCHzCHzOCHzN NCHzO CHzCHgCHgOHa 1 ,4-bis- (n-butoxymethyl) pip erazine Another similar type of hardener may be prepared by reacting a di-secondary amine with formaldehyde and an alcohol. For instance 22 grams of N,N'-dimethyl hexamethylene diamine was refluxed with 9 grams of paraformaldehyde, and 200 ml. of ethanol together with 200 ml. of benzene. Benzene-ethanol-water azeotrope was removed by distillation. The product, N,N'-bisethoxymethyl- N,N-dimethy1 hexamethylene diamine, was separated by distillation. It is a useful hardener for gelatin. Hardeners of this type may 'be represented by the formula:

wherein R and R are alkyl groups of 1-4 carbon atoms and n is Zto 10.

Although these hardeners are primarily of interest for incorporating into gelatin compositions to form hardened layers thereof, also contemplated are hardening proceconsidered as the most useful.

lowing:

useful as a hardener for gelatin,

Example 5 59.4 grams of 1,10-decanediol and 67.3 grams of 1,4-

bis(ethoxymethyl)piperazine were mixed and were stirred under nitrogen. The mass was then heated in a 175 C.

useful as a hardener for gelatin.

d h I 1 t t d 1 5 oil bath for 2 hours. Ethanol formed and was allowed to gf iz 253 1 3 2 31 533 ggg g gi distill off at atmospheric pressure. At the end of the 2 Eons or tie like Although Simpler typgcompoujlds co hogrsha vacuum pump was attalclfied 1tohthe relactlon flasl an t e reaction was contlnue or our. emov o g figgi g gggg zg Z i 2 3 2 3 33; fs gzi 2; the ethanol drives the reaction to completion. There was 10 l higher molecular weights such as greater than 150 are Obtamed a Polymeric mammal havmg the form a '-o CH OCHN NCH- Various methods of making hardeners useful in com- M 2 2 1 positions in accordance with the invention are the fol- Example 6 Exam 1 1 The same procedure was followed as described in the p e preceding example except that a 135 C. bath was em- 300 grams 10 moles) of paraformaldehyde were Ployed and grams of l f mlxed with 101 stirred into 1.5 liters of isobutanol. 400 grams of 40% grams l4'bls(.ethoxyr.nethyl)'p 1P erazme were used The aqueous methylamine were added with stirring. The mass Polymer: material obtamed had the formula: was refluxed and the isobutanol-water azeotrope was removed by means of a trap. When water was no longer O(CH)0CH2N Nome-1 f f g f s 5 z g f gi i There Both the materials in Examples 5 and 6 were found tobe ame 18 180 u Oxyme y me y amine w 16 1s 25 useful gelatin hardeners as was the product obtained when butanediol was employed in a like reaction. Example 2 The various hardeners referred to above are useful for hardening gelatin either in aqueous gelatin compositions 420 gums of piperazine were mixed with 300 grams or when present in gelatin-s1lver halide photographlc of paraformaldehyde in 3 liters of mbutanol and the mass emulsions. Because of the photographlc lnertness of these was refluxed. The water formed during the reaction was they are useful for hfirdenmg emu11ns wlthout removed as an n-butanol-water azeotrope by means of a producfng afiverse photographlc effects The hard trap w water was no longer formed, the product was eners lrsted 1n the followmg table were added to separate distilled. Obtained thereby was 1,4-bis(n-butoxymethyl)pi- Portions of a bromolodlde PP FP emulslon perazine. This material was useful as a hardener for m the E mdlcated Q g gq g i f s 61 he em 10 ed in a neon om Ton t onace ulose acetate support an r1 amp es o eac g a m w n p y q s c p051 1 5 here coating were then exposed on an Eastman 1b Sensrtometer and processed for 5 minutes in Kodak Developer DK-SO, Example 3 fixed, washed and dned with the indicated sens1tometr1c 311 grams of 2-arnino-2-hydroxymethyl-1,3-propanedi- 40 results. The coatings were also tested for swell properties 01 were mixed with 154 grams of paraformaldehyde and and melting point,

Gms. Melting Hardener hardener] Rel. 'y Fog Swell Point,

100 gms. Speed F.

gelatin Control 304 1 10 0.11 573 89 3-isobutoxymethyl-tetrahydro-1,3-oxazine 1 310 0 95 0.13 357 212 fi-hydroxmethyl-3,7-dioxa-1-azahicyclo[8.3.0]octane 1 293 0 90 0.10 200 200 5 288 0.80 0.10 126 200 the mass was refluxed in 500 ml. of toluene. The toluene- Samples of hardeners were added to separate portions water azeotrope formed was removed by means of a trap. of a sulfur and gold sensitized high speed silver bromoi- The cooled reaction mixture gave a crystalline product odide gelatin emulsion which had been panchromatically which was distilled to obtain 5-hydroxymethyl-3,7-dioxasensitized y the addition of a cyanine y The emulsion 1-azabicyclo[3.30]octane. This material was found to be Contained 245 grams of gelatin P mole of Silver halide- Each coating sample was coated on a cellulose acetate support at a coverage of 430 mg. of silver per square foot. Example 4 A sample of each coating was exposed on an Eastman 1b Sensitometer and processed for 5 minutes in Kodak 280 grams of paraformaldehyde were dissolved in 1.4 liters of isobutanol and 360 grams of 3-aminopropanol Developer DK-50, fixed, washed and dried with the following results:

1 Cone, Rel. Ret., Melt. Percent Hardener Gms./ Speed 7 Fog F. PL, Swell mole Ag F.

Control 100 1. 20 10 78 88 682 5-hyd roxymethyl-1-aza-3,7-d10xa b1eycl0(3.3.0)oetane 1 91 96 09 None 204 229 5 83 90 08 None 212 133 5-methyl-1-aza-3,7-d1oxa bicyclo(3.3.0)octaue 1 87 90 09 None 198 280 5 80 74 09 None 212 109 were added thereto. The mass was refluxed, the water being removed as the isobutanol azeotrope. By distillation, there was obtained 3-isobutoxymethyl-tetrahydro-1,3-oxazine which showed gelatin hardening properties when employed for that purpose,

These were added to gelatin-silver halide photographic emulsions polymeric hardeners as listed in the form of 2% solutions in methyl alcohol. These emulsion samples were then coated out onto a cellulose acetate film support and various tests were performed thereon in like manner as referred to in the previous examples. The results obtained were as follows:

z represents 2 or 3, each R represents a lower alkyl group, each m is an integer of 2-10, n is an integer of 2-10 and Gms. 100 Rel. Melting Percent Hardener gm. of Speed 1 Fog Point, Swell gelatin F.

Control 100 l. 20 0. ll 89 734 [(CH:|)2O CHaN NCHr-h 95 0. 55 0.37 211 182 [O (CHmOCHnN NCNa-h 5 100 0. 73 0.19 212 220 [-0 (CH2)sO CHzN NCHa-l: 5 95 0. 72 0. 19 212 226 Control 100 1. 0. 13 86 752 [-(O CzHmO CHN NCH:]: 6 89 0. 78 0. 07 212 156 i-(O C=H O CHBN NCH:] 2 3 76 0. 90 0. 09 212 257 [OCH=|CH,N NCH3CH:OCH:N NCHr-h 3 89 1.00 0. 07 202 227 The melting points of the gelatin coatings were determined by placing the samples in water and slowly heating the water to the point at which the layer disintegrates from the film base, this point being recorded. The swell measurements were made in a Carson Dice microdensitometer which is employed to measure the dry emulsion thickness. The sample is then immersed in distilled water at 68 F., removed from the water bath and then remeasured in the microdensitometer. The increase in thickness in terms of percentage is the swell value of the sample.

In the case of the polymeric hardeners in accordance with 'our invention, the degree of polymerization is not critical. The hardeners having a lower degree of polymerization are water-soluble while as the degree of polymerization increases the hardener material must be incorporated in the gelatin solution in the form of its solution in an organic solvent or in the form of an aqueous dispersion.

Polymeric hardeners in accordance with our invention can be used in photographic emulsions for use in difiFusion transfer processes such as those described in U.S. Patent No. 2,352,014 of Rott and in US. Patents Nos. 2,584,029, 2,698,236 and 2,543,181 of Land as well as in color transfer processes as described in Belgian Patents Nos. 554,933 and 554,934 of Polaroid and Belgian Patents Nos. 585,686 and 603,747 of Kodak.

We claim:

1. A composition of matter comprising gelatin containing a hardening amount of a compound selected from those having the formulas:

( 1 R'OCHQOCHZOR" (2) [-O (CH2)uO CHQYCHB-lx,

N-CHzCHzO CHaN wherein each R represents a lower alkyl group, Q represents R R Y represents-N N- or 'N(CH2)rnN-" each x is a number from 1 to 5,000 and wherein when x is l the terminal valence bonds are attached to hydrogen.

2. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula:

RO UH -N N-CH O R wherein each R represents a lower alkyl group.

3. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula:

R RO CHg-N-CHgOR' wherein R and R each represent a lower alkyl group.

4. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula:

R R R'OCH;N(CHz)...N-CH OR wherein each R and each R represent a lower alkyl group and m is an integer of 2-10.

5. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula:

[-0 (0 Hz) to C Hz-N N-CHz-l:

wherein n is an integer of 2-10, x is a number from 1 to 5,000 and wherein when x is 1 the terminal valence bonds are attached to hydrogen.

6. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula:

R R [o (CH2) nOCH2-N(C Hr)...N-0H,- wherein each R represents a lower alkyl group, m is an integer of 2-10, n is an integer of 2-10 and x is a number from 1 to 5,000 and wherein when x is l the terminal valence bonds are attached to hydrogen.

7. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula:

['(0C2H4)z0CH2-N NOHa-],

wherein 2 represents 2 or 3 and x is a number from 1 to 5,000 and wherein when x is l the terminal valence bonds are attached to hydrogen.

8. A composition of matter comprising gelatin containing a hardening amount of a compound having the formula: 1

[OCH:CH:N N-CHqCHgOCHr-N NCH:];

wherein x is a number from 1 to 5,000 and wherein when x is 1 the terminal valence bonds are attached to hydrogen.

9. A composition of matter comprising gelatin containing therein a hardening amount of 3-isobutoxymethyl oxazolidine.

10. A composition of matter comprising gelatin containing therein a hardening amount of a polymeric material consisting essentially of the recurring unit:

[-(oH,),oGH=-N \NCH2] 11. A composition of matter comprising gelatin containing therein a hardening amount of a polymeric material consisting essentially of the recurring unit:

12. A composition of matter comprising gelatin containing therein a hardening amount of a polymeric material consisting essentially of the recurring unit:

[-0 0 H2) 6 O C Hz-N N-C HP] 13. A composition of matter comprising gelatin containing therein a hardening amount of a polymeric material consisting essentially of the recurring unit:

[-OCHzCHz-h N-CHzCHaO CHz1 I\ N-CH2] 14. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 1.

15. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 2.

16. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 3.

17. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 4.

18. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 5.

19. A gelatin-silver halide photographicemulsion containing therein a hardening amount of a compound defined by claim 6.

20. A gelatin-silverhalide photographic emulsion containing therein a hardening amount of a compound defined by claim 7.

21. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 8. I

22. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 10.

23. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 11.

24. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 12.

25. A gelatin-silver halide photographic emulsion containing therein a hardening amount of a compound defined by claim 13.

References Cited UNITED STATES PATENTS 2/1962 Norwalk 260-6 4/1964 Harvey et al 260-6 NORMAN G. TORCHIN, Primary Examiner.

D. J. ARNOLD, Assistant Examiner. 

1. A COMPOSITION OF MATTER COMPRISING GELATIN CONTAINING A HARDENING AMOUNT OF A COMPOUND SELECTED FROM THOSE HAVING THE FORMULAS: 